BRPI0714518A2 - highly stable catalyst for heavy hydrocarbon hydrodesulfurization, methods for their manufacture and use and process for heavy hydrocarbon supply desulfurization - Google Patents

Abstract

HIGHLY STABLE CATALYST FOR HEAVY HYDROCARBON HYDRODUCURITY, METHODS FOR THE MANUFACTURING AND USE AND PROCESS FOR HEAVY HYDROCARBON SUPPLY. A catalyst useful in hydroprocessing a heavy hydrocarbon supply is disclosed wherein the catalyst comprises a calcined mixture produced by calcining a particle formed of a mixture comprising molybdenum trioxide, a nickel compound, and an inorganic oxide material. The catalyst can be produced by mixing an inorganic oxide material, molybdenum trioxide, and a nickel compound to form a mixture which is transformed into a particle and calcined to provide a calcined mixture. The process involves hydrodesulphurisation and hydro conversion of a heavy hydrocarbon supply process which may include converting a portion of the asphalt content of the heavy hydrocarbon supply and producing a treated product having improved stability as reflected by its value. -P.

Description

"HIGHLY STABLE CATALYST FOR HEAVY HYDROCARBON HYDRODUCURITY, METHODS FOR THE MANUFACTURE AND USE AND PROCESS FOR HEAVY HYDROCARBON SUPPLY"

This invention relates to a catalyst, a method of producing a catalyst.

and a process for producing a hydrocarbon product having low sulfur concentration. The invention further relates to a highly stable catalyst which is useful in hydrodesulphurisation of a heavy hydrocarbon supply, a method of producing a highly stable catalyst for use in hydrodesulphurization of a heavy hydrocarbon supply, and a process for hydrodesulphurization of heavy hydrocarbons. a heavy hydrocarbon product.

One process that is commonly recognized by those of ordinary skill in the hydrocarbon hydroprocessing art is the hydroconversion of heavy hydrocarbon supplies containing boiling point around 538 0C (1000 0F) to convert a portion of the heavy hydrocarbons. in the form of lighter hydrocarbons. It may also be desirable to simultaneously provide for the sulfur reduction of such heavy hydrocarbon supplies. Many of the conventional catalysts used to provide hydroconversion and desulphurisation of heavy hydrocarbon supplies contain a Group VIB1 metal component such as molybdenum and a Group VIII metal component such as cobalt or nickel supported on an oxide support. refractory.

US Patent No. 5,827,421 (Sherwood, Jr) discloses a process for hydroconversion and desulphurisation of a heavy hydrocarbon supply using an Alum supported catalyst containing Group VIII and Group VIB metals and having surface characteristics. and specifically defined pores. In this background section, this Patent provides intensive research and discussion of the existing technique and the in-house catalysts used in hydroconversion of heavy hydrocarbon supplies such as petroleum wastes and other heavy hydrocarbons. This Patent does not, however, provide any detail about the use of molybdenum trioxide as a necessary source of the molybdenum component of a hydroprocessing catalyst composition that is produced by a method including co-agglutination of trioxide. of molybdenum with an inorganic oxide material and a nickel compound.

US Patent No. 5,686,375 (Lyer et al.) Mentions hydroprocessing catalysts containing Group VIII metal components embedded with the preferred catalyst comprising a lower nickel bed and an upper molybdenum layer. The Patent states that many nickel and molybdenum compounds are useful for impregnation or coagglutination including molybdenum trioxide precursors, but it does not specifically mention co-agglutination of molybdenum trioxide with refractory support material. porous in the preparation of this catalyst support which has a built-in molybdenum component. However, the patent mentions the incorporation of molybdenum over the embedded nickel-containing support by co-agglutination rather than by impregnation. However, there is no guidance in '375 Patent on the preparation of a heavy hydrocarbon hydroconversion catalyst by co-agglutination can an inorganic support material with both molybdenum trioxide and a nickel compound followed by calcination of the resulting mixture to thereby form a material catalyst.

US Patent No. 6,030,915 (de Boer) discloses a hydroprocessing catalyst.

using fines from the regenerated depleted hydroprocessing catalyst in the manufacture of a hydroprocessing catalyst. The Patent further indicates that additional hydrogenation metals may be added to the impregnating catalyst composition using an impregnation solution comprising water-soluble salts of the hydrogenation metals to be incorporated into the catalyst composition. Also, an alternative method of incorporating the extra metal into the catalyst composition is indicated as including mixing the metal components either solid or dissolved with the fine mixture of regenerated depleted hydroprocessing catalyst, binder and optionally additive. Solid state metal may include solid molybdenum oxide. Additives are not indicated to be catalytic metal compound. In preparing its catalyst, '915 Patent requires the fines of the regenerated depleted hydroprocessing catalyst to be mixed with at least one additive, which may include a binder such as alumina, silica, silica-alumina, titania and clays.

It is desirable to have a catalyst which has a low production cost and is useful in hydrodesulfurizing a supply of heavy hydrocarbons, such as crude oil residue, while providing at least a conversion of at least portion of the heavy fraction of the heavy hydrocarbon supply to lighter hydrocarbons. It is further desirable that the desulphurized heavy hydrocarbon conversion product resulting from the use of the catalyst has highly stable properties as reflected by its P-value. It is also desirable for the hydroconversion catalyst to have a low deactivation rate at higher temperatures that are typically required to provide for conversion of the heavy fractions of a heavy hydrocarbon supply.

Accordingly, a highly stable catalyst for hydrocarbon sulfurization of heavy hydrocarbons is provided which comprises a calcined mixture produced by calcining a particle formed of a mixture comprising molybdenum trioxide, a nickel compound, and an inorganic oxide material. Such a highly stable heavy hydrocarbon hydrodesulfurization catalyst may be produced by the method comprising: co-agglutination of an inorganic oxide material, molybdenum trioxide, and a nickel compound to form a mixture; transforming said mixture into a particle; and calcining said particle to provide a calcined mixture. The highly stable catalyst for heavy hydrocarbon desulphurisation may additionally be used in a process for desulphurizing a heavy hydrocarbon supply, wherein said process comprises: contacting, under suitable conditions of heavy hydrocarbon desulphurization, a supply heavy hydrocarbons with a heavy hydrocarbon hydrodesulfurization catalyst comprising a calcined mixture produced by calcining a particle formed of a mixture comprising molybdenum trioxide, a nickel compound, and an inorganic oxide material; and produce a desulphurized product.

Figure 1 presents a graph of the P-value of the product produced from hydrocarbon processing of heavy hydrocarbon supplies when using the inventive catalyst as compared to a comparative catalyst as a function of asphalt conversion. As can be seen from the two graphs, the inventive catalyst provides for a product having a higher P-value than that provided by the comparative catalyst and thus a more stable product.

Figure 2 shows comparison charts of relative values for Weighted Average Bed Temperature (WABT) calculated as a function of time for 88% hydrofabrication of a heavy supply using the inventive catalyst as compared to a comparative catalyst. The slope of the graphs provide an indication of the stability of catalyst activity, and the relative positions of the two graphs reflect the relative catalytic activity of the catalysts.

A new catalyst composition has been discovered that is especially useful in

desulfurization and hydroconversion of heavy hydrocarbon streams containing sulfur and heavy hydrocarbons having a boiling temperature greater than 538 0C (1000 0F). This catalyst composition exhibits exceptional stability in its desulphurization activity even though it is used under process conditions with temperatures higher than those typically used for hydrodesulphurization to provide for a high conversion of the heavy hydrocarbons contained in the heavy hydrocarbon stream that is present. It is to be processed or treated. Also, the catalyst composition provides for a desulfurized hydroconverted product which exhibits high stability in that it has a low tendency to flocculation as compared to hydroconverted products resulting from the use of alternative catalysts. Apart from the numerous catalytic and process advantages that the new catalyst provides, it also has low production cost due to the new method of producing the catalyst composition. The inventive catalyst composition comprises a calcined mixture which is produced by calcining a particle formed of a mixture comprising molybdenum trioxide, a nickel compound, and an inorganic oxide material. It is an essential aspect of the invention for at least a larger portion of the molybdenum component of the inventive catalyst to be supplied by molybdenum trioxide as opposed to molybdenum trioxide precursors such as some of the molybdenum salts, for example ammonium dimolibdate, and ammonium heptamolybdate. And, indeed, it is an important aspect of the invention for the mixture from which the particle is formed to be made using molybdenum trioxide. It is preferred for the molybdenum trioxide used in forming the mixture to be in the form of a finely defined powder, which may be in a liquid suspension or flowing pulp. Therefore, the mixture that is transformed into a particle and thereafter calcined may comprise a substantial absence of a molybdenum compound which is in another form such as molybdenum trioxide, such as, for example, a molybdenum salt compound. nio.

What is meant here when referring to the substantial absence of a compound

molybdenum in a form other than as molybdenum trioxide is that the mixture that is shaped or formed into a particle configured and then calcined under suitable calcining conditions, as more fully described elsewhere below, contains less than a small or less that a negligible amount of a molybdenum compound other than molybdenum trioxide, such as, for example, a molybdenum salt compound or an inorganic molybdenum compound. Examples of molybdenum compounds other than molybdenum trioxide include ammonium molybdate, ammonium dimolybdate, ammonium heptamolybdate, molybdenum acetate, molybdenum bromide, molybdenum chloride, molybdenum carbide and molybdenum carbide. It is therefore desirable for a mixture to contain less than 2 weight percent, based on the total weight of the mixture, of a molybdenum compound other than molybdenum trioxide. It is preferred for the mixture to contain less than 1 weight percent of a molybdenum compound other than molybdenum trioxide, and most preferably less than 0.5 weight percent.

In another embodiment of the invention, the mixture may consist essentially of molybdenum trioxide, a nickel compound, and an inorganic oxide material. As used herein, the phrase "essentially consists of," similar phraseology, is used in the definition of elements or components that constitute a mixture, meaning that a material amount of any molybdenum compound other than molybdenum trioxide is excluded from the mixture. . This phrase, however, is not intended to mean that material components of other components such as promoter components including phosphorus compounds are excluded from said mixing components. A material amount of a molybdenum compound other than molybdenum trioxide is an amount of such a compound contained in the mixture which provides for a material effect according to the catalytic performance properties of the final catalyst. These catalyst performance properties are discussed in more detail below.

The amount of molybdenum trioxide contained in the mixture should be such as to provide a final calcined mixture having a molybdenum content in the range of over 12 weight percent as metal (18% wt based on MOO3). ), with the percentage by weight being based on the total weight of the calcined mixture. However, it is desirable that the amount of molybdenum trioxide contained in the mixture be such as to provide a final calcined mixture having a molybdenum content in the range of from 4 to 11% w as metal ( 6 to 16.5 wt% as oxide), more preferably from 5 to wt% (7.5 to 15 wt% as oxide), and most preferably from 6 to 9 wt% (9 to 13.5 % p as oxide).

In addition to the molybdenum trioxide component, the mixture additionally contains a nickel compound. The source of the nickel component of the mixture is not crucial to the manufacture of the inventive catalyst as the source of the molybdenum component, and thus the nickel component can be selected from any suitable nickel-mixable compound. with the other components of the mixture and be shaped into a particle that is to be calcined to form a final calcined mixture. Nickel compounds may include, for example, nickel hydroxides, nickel nitrates, nickel acetates, and nickel oxides.

The amount of nickel compound contained in the mixture should be such as to provide a final calcined mixture having a nickel content in the range above 4 weight percent as metal (5.1 wt% NiO based). , with the percentage by weight being based on the total weight of the calcined mixture. However, it is desirable that the amount of the nickel compound contained in the mixture be such as to provide a final calcined mixture having nickel content in the range of from 0.5 to 3.5% w as metal ( 0.64 to 4.45 wt% as oxide), more preferably from 1 to 3 wt% (1.27 to 3.82 wt% as oxide), and most preferably from 1.5 to 2, 5 wt% (1.91 to 3.18 wt% as oxide).

In addition to the molybdenum trioxide component and the nickel compound, the mixture additionally includes an inorganic oxide material. Any porous inorganic refractory oxide that can provide the required surface structural properties required for the inventive catalyst can be used as the inorganic oxide material component of the mixture. Possible examples of suitable types of porous inorganic refractory oxides include silica, alumina, and silica alumina. Preferred is either alumina or silica alumina.

The amount of inorganic oxide material that is contained in the mixture is such as to provide an amount in the range of from 50 to 95 weight percent inorganic oxide material in the final calcined mixture with the weight percent being with based on the total weight of the calcined mixture. Preferably, the amount of inorganic oxide material in the calcined mixture is in the range of from 60 to 92 weight percent, and most preferably from 70 to 89 weight percent.

In addition to the requirement that the source of the molybdenum component of

Since the inventive catalyst is to be predominantly provided by molybdenum trioxide, the surface characteristics of the inventive catalyst may also be important for its performance in hydroconversion and desulphurisation of a sulfur-containing heavy hydrocarbon supply stream. It is important for the inventive catalyst to have an average pore diameter that is within a narrow specific range and to have low macroporosity as described below. In order to provide the desired catalytic properties, the average pore diameter of the inventive catalyst is generally in the range of from 85 angstroms (Â) to 100 Â °. Preferably, the average pore diameter is in the range of from 86 to 98 angstroms, and most preferably from 87 to 97 angstroms.

The inventive catalyst should, in addition to having an average pore diameter that is within the narrow and specific range as discussed above, also have a low macroporosity where a small percentage of the total catalyst pore volume is contained in the inventive catalyst macropores. . The term macropore is defined as a catalyst pore of a catalyst composition having a diameter greater than 350 angstroms. It is preferred that the inventive catalyst has a low macro porosity such that less than 4.5 percent of the total pore volume is contained in its macropores, but more preferred is that less than 4 percent of the total pore volume is contained in its pores. macropores, and most preferably less than 3.5 percent of the total volume of is contained in their macropores. Also, it is desirable that the pore structure of the inventive catalyst be such that less than 1 percent of the total pore volume to be contained in its macropores has a diameter greater than 1000 angstroms, and is more desirable than less than 0, 9 percent of the total pore volume to be contained in macropores has a diameter greater than 1000 angstroms, and it is very desirable that less than 0.8 percent of the total pore volume to be contained in macropores has a diameter greater than 1000 angstroms. angstroms.

An additionally important property of the inventive catalyst is that it has a significantly high surface area. It is the particular combination of a significantly high surface area in combination with the narrow distribution of pore diameters and the use of molybdenum trioxide as the source of molybdenum in the manufacture of the inventive catalyst that contributes to many of the important performance properties. of the inventive catalyst. It is desirable for the inventive catalyst to have a reasonably high surface area exceeding 230 m2 / g. Preferably, the surface area of the inventive catalyst exceeds 240 m 2 / g, and most preferably it exceeds 250 m 2 / g.

The inventive method has been found to provide a novel catalyst which, as noted above, has particularly good properties when it is used in the dual function of hydrodesulfurization and hydroconversion of a heavy hydrocarbon stream containing both a sulfur and hydrocarbon concentration. heavy. Although it is not known for certain, many of the beneficial catalytic properties of the inventive catalyst are believed to be associated with the new catalyst manufacturing method and also the use of molybdenum trioxide as the main source of the molybdenum component of the catalyst. catalyst as opposed to the use of alternative sources of molybdenum in such fabrications. It is to be assumed that the reason for this is in some way associated with molybdenum trioxide having acidic properties and other unique properties such that when combined with alumina it is more effectively incorporated and properly dispersed. inside the alumina matrix. In fact, electron scanner examination of certain micrographs of the inventive sulfide catalyst suggests that there is a significantly lower degree of stacking of molybdenum disulfide plates (MoS2) having reduced heights and lengths as compared to catalysts. molybdenum hydroprocessing alternatives.

The inventive method for producing the catalyst of the invention includes mixing the appropriate starting materials to form a mixture which is transformed or agglomerated into particles which are then calcined to thereby provide a calcined mixture. The calcined mixture itself may be used as the highly stable double function catalyst, hydroconversion and hydrodesulfurization, or it may be activated before or during use by a number of known methods including hydrogen or sulfur treatment or sulfur compounds. such as elemental sulfur, hydrogen sulfide or an organic sulfur compound. The first step of the inventive method includes combining the catalyst starting materials to form a mixture. Essential starting materials in the preparation of the mixture include molybdenum trioxide which is preferably in the form of finely divided particles which may be as dry powder or as particles in a suspension or fluid pulp, and an inorganic oxide material such as oxide material. inorganic material selected from the group consisting of alumina, silica and alumina-silica. Also, a nickel component may additionally be combined with molybdenum trioxide and inorganic oxide material in the mixture formation. The nickel component may be selected from any suitable source of nickel including nickel salt compounds, either dried or dissolved in solution, or any other nickel compound including those mentioned above.

Mixing may be accomplished by any method or means known to those of ordinary skill in the art, including, but not limited to, the use of such suitable types of solid mixing machines such as tippers, hulls or stationary troughs, grinder mixers, which are either batch or continuous type, and impact mixers, and the use of such suitable types of either batch or continuous mixers for mixing solids and liquids or for the formation of pasty type mixtures which are possible for extrusion. Suitable types of batch mixers include, but are not limited to, cup change mixers, stationary tank mixers, double arm kneading mixers that are equipped with any type of mixing blade. Suitable types of continuous mixers include, but are not limited to, single or double screw extruders, trough and screw mixers, and mortar mills.

Mixing of catalyst starting materials may be conducted for any suitable period of time necessary to properly homogenize the mixture. Generally, the mixing time may be in the range of about 2 hours or more than 3 hours. Typically, the mixing time is in the range of from 0.1 hour to 3 hours. The term "co-agglutination" is used broadly in this specification to mean that at least the mentioned starting materials are mixed together to form a mixture of the individual components of the mixture which is preferably a substantially uniform or homogeneous mixture of the individual components. of such a mixture. Such a term is intended to be broad enough in scope to include mixing the starting materials to produce a paste having properties that make it capable of being extruded or extruded particles by any of the known extrusion methods. However, the term is also intended to encompass mixing of the starting materials to produce a mixture which is preferably substantially homogeneous and capable of being agglomerated in the form of configured particles, such as sphericals, pills or tablets, cylinders, irregular extrusions or simply loosely bonded agglomerated aggregates by any of the methods known to those of ordinary skill in the art, including, but not limited to, molding, tableting, pressing, agglutination, extrusion and tipping. As already noted, it is an important aspect of the inventive method that at least

a larger portion of the catalyst molybdenum source is predominantly molybdenum trioxide. In mixing or co-agglutination of the catalyst starting materials, it is preferred that molybdenum trioxide is in a finely divided state either as a finely pulverized solid or as fine particles in a slurry or slurry. It is better for the particle sizes of molybdenum trioxide used in the manufacture of the catalyst to have a maximum dimension of less than 0.5 mm (500 micron, pm), preferably a maximum dimension of less than 0, 15 mm (150 µm), more preferably less than 0.1 mm (100 µm), and most preferably less than 0.075 mm (75 µm).

Although not known for certain, it is believed to be advantageous for the invention that molybdenum trioxide that is used in the manufacture of the inventive catalyst is in the form of particles as small as practically possible; Therefore, it is not desirable to have a lower limit on the size of the molybdenum trioxide particles used in the manufacture of the catalyst. However, it is understood that the particle size of the molybdenum trioxide used in the manufacture of the catalyst will generally have a lower limit for its size of more than 0.2 microns. Thus, the particle size of molybdenum trioxide used in forming the mixture in the manufacture of the inventive catalyst is preferably in the range from 0.2 to 150 µm, more preferably from 0.3 to 100 µm. ym, and most preferably from 0.5 to 75 µm. Typically, the size distribution of molybdenum trioxide particles, whether in dry powder or a suspension or otherwise, is such that at least 50 percent of the particles have a maximum size in the range of from 2 to 15 / ym. Once catalyst starting materials are properly mixed

and transformed into the shaped or shaped particles, a drying step may advantageously be used to remove certain amounts of water or volatiles that are included in the mixture or particles formed. Drying of the formed particles may be conducted at any suitable temperature to remove excess water or volatiles, more preferably, the drying temperature will be in the range of from about 75 ° C to 250 ° C. The time period for drying the particles is any suitable period of time required to provide the desired amount of reduction in particulate volatiles prior to the calcination step.

Dry or non-dried particles are calcined in the presence of a fluid containing oxygen, such as air at a temperature that is suitable to achieve a desired degree of calcination. Generally, the calcination temperature is in the range of from 450 0C (842 0F) to 760 0C (1400 ° F). The temperature conditions under which the particles are calcined may be important for controlling the pore structure of the final calcined mixture. Due to the presence of molybdenum trioxide in the particles formed, the calcination temperature required to provide a calcined mixture having the required pore structure is higher than the typical temperatures required to calcine other compositions containing inorganic oxide materials, especially those. not containing molybdenum trioxide. However, in any case, the temperature at which the particles formed are calcined to provide the finally calcined mixture is controlled to provide the finally calcined mixture having the properties of the pore structure as described in detail herein. The preferred calcination temperature ranges from 510 ° C (950 ° F) to 730 ° C (1346 ° F), and most preferably from 540 ° C (10040 ° F) to 705 ° C (1301 ° F).

The calcined mixture is particularly useful as a high stability catalyst for hydroprocessing for use in hydroprocessing a heavy supply stream having high asphalt and sulfur contents. Prior to use, the calcined mixture may, however, not necessarily be sulphide or activated by any of the methods known to those of ordinary skill in the art. Generally, in its use in hydroprocessing a hydrocarbon supply, the calcined mixture is contained within a reaction zone, such as that defined by a reactor vessel, where a hydrocarbon supply is contacted with the calcined mixture under suitable conditions of the hydroprocessing reaction and from which a treated hydrocarbon product is produced.

The preferred hydrocarbon supply of the inventive process is a heavy hydrocarbon supply. The supply of heavy hydrocarbons may be derived from any high boiling temperature oil cuts such as atmospheric tower gas oils, atmospheric tower bottom residues, vacuum tower gas oils, and vacuum tower bottom residues, or waste. It is a particularly useful aspect of the inventive process that hydroprocessing of a heavy hydrocarbon supply can generally be defined as having a boiling temperature at its distillation point 5%, ie T (5), above 300 ° C (572 0F) as determined using the test procedure set forth in ASTM D-1160. The invention is more particularly directed to hydroprocessing a heavy hydrocarbon supply having a T (5) exceeding 315 ° C (599 ° F) and still one exceeding 340 ° C (644 ° F).

The supply of heavy hydrocarbons may additionally include heavier hydrocarbons having boiling temperatures above 538 ° C (1000 ° F). Such heavier hydrocarbons are referred to herein as asphalts, and, as already indicated, it is recognized that one of the special features of the inventive catalyst or process is that it is particularly effective in hydroconverting the asphalt content of a heavy hydrocarbon supply. . The supply of heavy hydrocarbons may include as little as 10 percent by volume of asphalt or as much as 90 percent by volume of asphalt, but generally, the amount of asphalt included in the heavy hydrocarbon supply is in the range from 20 to 80 percent by volume. And, more typically, the asphalt content in the heavy hydrocarbon supply ranges from 30 to 75 percent by volume.

The supply of heavy hydrocarbons may additionally include a content of

sulfur significantly high. One of the special features of the invention is that it provides for both the desulphurisation of the heavy hydrocarbon supply and the conversion of asphalts to lighter hydrocarbons having lower boiling temperatures than those of asphalt hydrocarbons. The sulfur content of the heavy hydrocarbon supply is primarily in the form of sulfur-containing organic compounds, which may include, for example, substituted or unsubstituted mercaptans, thiophene, heterocyclic compounds, or any other type of sulfur-containing compound. fre.

A feature of the invention is that it provides desulphurisation of the heavy supply having a significantly high sulfur content, such as a sulfur content greater than 1 percent by weight, to provide a treated hydrocarbon product having a sulfur content. reduced sulfur content, such as a sulfur content of less than 1 weight percent. When referring here to the sulfur content of either the heavy hydrocarbon supply or the treated hydrocarbon product, weight percentages are determined using the ASTM D-4294 test method. The inventive process is particularly useful in processing a heavy hydrocarbon supply having a sulfur content in excess of 2 percent by weight, and with such a heavy hydrocarbon supply the sulfur content may be in the range of from 2 to 8 weight percent. The inventive catalyst and process is especially useful in processing a heavy hydrocarbon supply having an especially high sulfur content exceeding 3 or even 4 weight percent and ranging from 3 to 7 weight percent or more. from 4 to 6.5 weight percent.

The inventive process utilizes the inventive catalyst in hydroprocessing the heavy hydrocarbon supply to provide simultaneous desulphurization and conversion of asphalt to produce the treated hydrocarbon product having low sulfur and asphalt contents. In this process, the supply of heavy hydrocarbons is contacted with the inventive catalyst under suitable hydrodesulfurization and hydroconversion process conditions and the treated hydrocarbon product is produced. The treated hydrocarbon product should have a low sulfur content that is below that of the heavy hydrocarbon supply, such as a sulfur content of less than 1 weight percent. It is preferred that the sulfur content of the treated hydrocarbon product is less than 0.8 weight percent, and most preferably less than 0.6 weight percent. It is identified that the inventive process, however, may have the ability to effectively desulfurize the heavy hydrocarbon supply to provide the treated hydrocarbon product having a reduced sulfur content of less than 0.5 and even less than 0.4 percent by weight. Weight.

The inventive process may additionally provide a conversion of a

portion of the asphalt content of the heavy hydrocarbon supply. When referring here to asphalt conversion or asphalt conversion or other similar terminology, it is meant that a portion of the hydrocarbons contained in the heavy hydrocarbon supply having a boiling temperature exceeding 538 0C (1000 0F) is converted. hydrocarbons having a boiling temperature of less than 538 ° C (1000 ° F). In a preferred embodiment of the inventive process, the asphalt conversion is greater than 20 percent by volume of the asphalt contained in the heavy hydrocarbon supply, and more preferably the asphalt conversion exceeds 30 percent by volume. Most preferably, the asphalt conversion exceeds 40 percent by volume of the asphalt contained in the heavy hydrocarbon supply. A practical upper limit for asphalt conversion is 90 percent by volume, and more typically the upper limit for asphalt conversion is 60 percent by volume. Thus, asphalt conversion, for example, may be in the range of from 20 to 90 percent by volume, or from 30 to 60 percent by volume, or from 40 to 60 percent by volume.

At higher asphalt conversion levels the quality of the hydrocarbon product tends to suffer. This is believed to be due to the agglomeration of the asphaltenes structures contained in the heavy hydrocarbon supply being processed. Such agglomeration may, under extreme conditions, result in the separation of the solid fraction from the treated hydrocarbon product and settlement or deposition of solids on the surfaces of process equipment. In general, the upper limit of asphalt conversion is the point at which precipitation of the product begins to emerge. Several techniques have been used in the oil processing industry to predict the onset of such precipitation, including unique testing methods and the P-value test which is described more fully below.

One of the advantages provided by the high asphalt conversion of the inventive process is that it results in the production of the treated hydrocarbon product having hydrocarbons having boiling temperatures in the naphtha, distillates (dieel and kerosene), and vacuum gas oil temperature ranges. These produced products may be mixed with the product streams produced by other refinery process units or they may be further processed. For example, the inventive process distillates may additionally undergo hydroprocessing to produce products such as kerosene, jet fuel and diesel, and the inventive process vacuum gas oil may be used as a supply for a refining unit. such as a fluid catalytic cracking unit or a hydrocracking unit. Depending on the particular market conditions, the distilled fraction produced from the inventive process can be especially valuable, thereby producing a higher yield of distillates as opposed to the highly desirable higher naphtha yields and vacuum gas oil.

In addition to providing significant conversion of the heavy hydrocarbon supply asphalt content, the inventive catalyst and process may provide incrementally greater yield of the distilled product than alternative catalysts and processes, and thus they may provide benefits. larger than the other alternatives. The inventive process may additionally provide a higher proportion of heavy hydrocarbon supply asphalt which is converted to hydrocarbons having a boiling temperature of less than 538 ° C (1000 ° F) which is converted to hydrocarbons with boiling points in the boiling range of the distillates. 180 ° C (356 ° F) to 350 ° C (662 0F), or to distilled hydrocarbons. The inventive process thus can provide a treated hydrocarbon product, wherein the proportion of converted asphalts including boiling hydrocarbons in the boiling range of distillates exceeds 10 percent by weight of the converted asphalts. The inventive process preferably provides a treated hydrocarbon product that includes a proportion of converted asphalt that includes hydrocarbons with boiling points in the boiling range of distillates that exceed 14 percent by weight of converted asphalts, more preferably exceeding 16 per cent by weight of converted asphalts and most preferably in excess of 18 per cent by weight of converted asphalts. This feature of the inventive process is particularly beneficial when, in combination with other processes, an ultra low sulfur diesel product is manufactured. This benefit is due to the high amount of distilled product produced having a relatively low sulfur content that makes even more severe hydroprocessing unnecessary to produce low sulfur diesel product. However, mild hydrodesulfurization processing may be required.

Another feature of the inventive process is that, in addition to providing desulphurisation and asphalt conversion, it can provide a significant reduction in the Micro-Carbon Residual (MCR) content of the treated hydrocarbon product of the process using the inventive catalyst. . Residual Microcarbon Content refers to an amount of carbon residue that remains after evaporation and pyrolysis of a substrate and is determined using the ASTM D4530 test method. In cases where the heavy hydrocarbon supply has a significant MCR1 content the inventive process may provide a treated hydrocarbon product having a MCR content that is below that of the heavy hydrocarbon supply, and indeed the inventive catalyst. may provide a greater reduction in MCR content than other catalysts already in the art. Such an improvement in the ability to reduce the MCR content of a supply is particularly advantageous in those situations when the inventive process is to provide a treated hydrocarbon product that is to be used, or parts of it to be used, as a supply for a supply. fluid catalytic cracking unit (FCC). This benefit is recognized by the fact that the MCR content of an FCC supply can significantly impact the amount of such supply that the FCC unit is capable of processing. In general, an FCC unit is capable of processing larger quantities of supplies that have lower MCR levels than those that have higher MCR levels.

In the inventive process, the supply of heavy hydrocarbons may have a value of

MCR exceeding 6%. The inventive process is particularly useful in processing a heavy hydrocarbon supply having an MCR value exceeding 8% and still exceeding 10%. The treated hydrocarbon product may have an MCR value of less than 6%, preferably less than 5%, and more preferably less than 4%. A disadvantage of using existing hydroconversion catalysts in

Conversion of heavy hydrocarbon supplies is that the resulting product will tend to have a low P-value. The P-value (peptization value) is a numerical value that is an indicator of the flocculation tendency of asphaltenes contained in a hydrocarbon mixture. The determination of the P-value is by the method as described by J. J. Heithaus in "Measurement and Significance of Asphaltene Peptization", Journal of Institute of Petroleum, Vol. 48, Number 458, February 1962, p. 45-53, the publication of which is hereby incorporated by reference.

A high P-value for a hydrocarbon mixture indicates that it is stable and a low P-value for a hydrocarbon mixture indicates that it is not as stable because there is a greater tendency for precipitation of asphaltenes contained in the hydrocarbon mixture. Nice. It is identified that the P-value of a hydroconverted product tends to decline as the percentage of the asphalt component of a converted heavy hydrocarbon supply increases, thereby indicating a greater tendency for precipitate formation. . However, it is one of the advantages of the inventive catalyst and process that they provide a high amount of asphalt conversion while providing a treated hydrocarbon product that still has an exceptionally high P-value exceeding 1.25. The catalyst and process may provide an asphalt conversion of more than 30 percent by volume while providing a treated hydrocarbon product having a P-value greater than 1.25. It is preferred for the P-value of the treated hydrocarbon product to exceed 1.5, more preferably exceed 1.75, and most preferably exceed 2 when the asphalt conversion of the heavy hydrocarbon supply that is provided by the inventive catalyst and process exceeds 30 percent by volume. In some cases, the P-value of the heavy hydrocarbon supply may be less than 1.

The calcined mixture (catalyst) of the invention may be employed as a part

any suitable reactor system that provides catalyst contact with heavy hydrocarbon supply under suitable hydroprocessing conditions which may include the presence of hydrogen and a high total pressure and temperature. Such suitable reaction systems may include fixed bed catalyst systems, boiling bed catalyst systems, pasty catalyst systems, and fluidized bed catalyst system. The preferred reaction system is that which includes a fixed bed of inventive catalyst contained within the reaction vessel equipped with reactor feed input means, such as a feed nozzle, for introducing the supply of heavy hydrocarbons into the reaction vessel, and reactor effluent outlet means, such as a reactor effluent outlet nozzle, for withdrawing reactor effluent or treated hydrocarbon product from the reaction vessel. The inventive process generally operates at a hydroprocessing reaction pressure.

(hydroconversion and hydrodesulfurization) in the range from 2068 kPa (300 psig) to 20,684 kPa (3000 psig), preferably from 10,342 kPa (1500 psig) to 17,237 kPa (2500 psig), and more preferably from 12,411 kPa (1800 psig) at 15,513 kPa (2250 psig).

The hydroprocessing reaction temperature is generally in the range from 340 ° C (644 ° F) to 480 ° C (896 ° F), preferably from 360 ° C (680 ° F) to 455 ° C (851 ° F), and most preferably. from 380 ° C (7160F) to 425 ° C (797 0F).

The flow rate at which the heavy hydrocarbon supply is charged to the reaction zone of the inventive process is generally such as to provide a net hourly space velocity (LHSV) in the range of from 0.01 h to 1 to 3 h '. 1. The term "net hourly space velocity" as used herein means a numerical ratio of the rate at which the heavy hydrocarbon supply is carried to the reaction zone of the inventive process in volume per hour divided by the catalyst volume contained in the zone. which the heavy hydrocarbon supply is loaded The preferred LHSV is in the range of from 0.05h "1 to 2h" 1, more preferably 0.1h "1 to 1.5h "1, and most preferably from 0.2 h" 1 to 0.7 h "1.

It is preferred to carry hydrogen along with the heavy hydrocarbon supply to the reaction zone of the inventive process. In this case, hydrogen is sometimes referred to as a hydrogen treatment gas. The hydrogen treatment gas rate is the amount of hydrogen relative to the amount of heavy hydrocarbon supply charged to the reaction zone and is generally in the range above 1781 m3 / m3 (10,000 SCF / bbl). It is preferred for the treatment rate to be in the range of from 89 m3 / m3 (500 SCF / bbl) to 1781 m3 / m3 (10,000 SCF / bbl), more preferably from 178 m3 / m3 (1,000 SCF / bbl) at 1602 m3 / m3 (9,000 SCF / bbl), and most preferably from 356 m3 / m3 (2,000 SCF / bbl) to 1425 m3 / m3 (8,000 SCF / bbl). The following examples are presented to further illustrate the invention,

however, they are not to be considered as limiting the scope of the invention.

Example I This Example I describes the preparation of Catalyst A.

Catalyst A

Catalyst A was prepared by first combining 3209 parts by weight 2% alumina interstage silica, 287 parts by weight nickel (Ni (NO3) 2) nitrate dissolved in 99 parts by weight deionized water, 269 parts by weight trioxide of molybdenum powder (MOO3) 1 and 652 parts by weight of reclaimed Ni / Mo / P hydrotreating catalyst crushed into a Muller mixer together with 130 parts by weight of 69.9% concentrated nitric acid of a commercial extrusion aid. A total of 2948 parts by weight of water were added to these components during mixing. The components were mixed for approximately 40 minutes. The mixture had a pH of 4.08 and a LOI of 55.7 weight percent. The mixture was then extruded using 1.3 mm trilobal dies to form 1.3 mm trilobal extruded particles. The extruded particles were then air dried over a period of several hours at a temperature of 100 ° C.

Aliquots of the dried extruded particles were calcined in air each

one for a period of two hours at a temperature of 426 ° C (800 ° F), 566 ° C (1050 ° F), 677 ° C (1250 ° F), or 732 ° C (1350 ° F). The final calcined mixture contained 2.2 weight percent nickel metal (2.8 wt% as NiO), 7.9 weight percent molybdenum metal (11.85 wt% as MOO3) and 85.45 weight percent 2% silica / alumina. Table 1 below shows some properties of the dried extruded particles that were calcined at each of the calcining temperatures. As can be seen from the pore properties shown in Table 1, the percentage of the total pore volume contained in macropores having a pore diameter of 1000 Angstroms and larger is less than 1 percent.

Table 1 - Properties of Dry Extruded for Different Calcine Conditions-

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Properties 426 0C (800 0F) 566 0C (1050 0F) 677 0C (1250 0F) 732 0C (1350 ° F) Surface Area m2 / g 332 311 256 133,5 Pore Size Distribution Hg (A) Less than 70 38.8 28.3 9.8 0.8 70-100 41.2 50.1 48.7 1.6 100-150 12.2 13.5 31.3 18.3 150-350 5, 7 6.0 7.5 66.9 350-1000 1.9 1.9 2.0 11.1 1000+ 0.2 0.2 0.7 0.3 Total pore volume, cc / g 0.551 0.564 0.596 0.702 Average Pore Diameter, Â 76 81 96 128

Example Il (Example of Constant Sulfur Conversion)

This Example II describes one of the methods used to perform the tests of the catalysts described in Example I. This method provided the processing of a supply having a significant sulfur concentration to produce a product having a specified sulfur concentration. The reactor temperature was adjusted to keep the sulfur concentration in the reactor product fixed.

Catalyst A and a commercially available hydrodemetallization catalyst were loaded into a 1.5875 cm (5/8 inch) ID by 127 cm (50 inch) stainless steel tubular reactor in a stacked 66.7-byte bed arrangement. percent by volume of the bed consisting of catalyst A placed at the bottom of the catalyst bed and 33.3 percent by volume of the bed consisting of hydrodemetallization catalyst placed on top of the catalyst bed.

The tubular reactor was equipped with thermocouples placed in a 0.635 cm (1/4 inch) thermometer cavity concentrically into the catalyst bed, and the tubular reactor was kept inside a 132 cm (52 inch) 5 zone oven ) with each zone being separately controlled based on a signal from a thermocouple.

The stacked catalyst bed catalyst was activated by feeding into the ambient pressure a 5% v H2S and 95% v H2 gas mixture to the reactor at a rate of 1.5 LHSV while incrementally increasing the reactor temperature by a from 37.80 ° C (100 ° F) / h to 204.4 ° C (400 ° F). The catalyst bed was maintained at 204.4 ° C (400 ° F) for two hours and then the temperature was increased incrementally at a rate of 37.8 ° C (100 ° F) / h to a temperature of 315 ° C. 50 ° C (600 ° F), where it was maintained for one hour followed again by an incremental temperature increase at a rate of 23.9 ° C (75 ° F) / h to a temperature of 371.10 ° C ( 700 ° F), where it was held for two hours before cooling the catalyst bed temperature to room temperature. The catalyst bed was then pressurized with pure hydrogen at 6,895 kPa (1000 psig), and the catalyst bed temperature was incrementally increased at a rate of 37.8 ° C (100 ° F) / h to 204.4 ° C (400 ° F). ). The reactor was then charged with supply while the reactor temperature was maintained at 204.40 ° C (400 ° F) for one hour. The catalyst bed temperature was then incrementally increased at a rate of 10 ° C (50 ° F) / hr to 371.10 ° C (700 ° F), from which point the race was started. The supply loaded to the reactor was a Middle East oil production residue. The distillation properties of the supply as determined by the ASTM D7169 Method are shown in Table 2. Table 3 presents some other supply properties. Table 2 - Supply Distillation

% p Temperature 0C (0F) IBP 273 (523) 377 (711) 427 (801) 466 (871) 40 503 (937) 50 543 (1009) 60 588 (1090) 70 636 (1177) 80 695 (1283) 90 FBP 737 (1359) Table 3 - Other Supply Properties Property Value Residue Micro-Carbon (MCR) 12.4 Sulfur (% w) 4.544 Nickel (ppm) 22 Vanadium (ppm) 75 537.8 0C (1000 ° F) + (% v) 51.3

The supply was charged to the reactor along with hydrogen gas. The reactor was maintained at a pressure of 13,100 kPa (1900 psig) and the supply was charged to the reactor at a rate to provide a net hourly space velocity (LHSV) of 0.33 h "1 and hydrogen was charged at a rate of 534. m 3 / m 3 (3,000 SCF / bbl) The temperature of the reactor was adjusted to provide a product having a sulfur content of 0.52 wt%.

Inventive catalyst A provides a product having a significantly reduced sulfur content over the sulfur content of the processed supply. The sulfur content of the product was less than 0.6 weight percent with the catalyst hydrodesulfurization activity remaining stable over a significant period of time.

Example III This Example III describes the preparation of Catalyst B. Catalyst B Catalyst B was prepared by first dissolving 252 parts by weight of Ni (NO 3) 2-6H 2 O in 87 parts of deionized water and heating the solution to cleanness. Separately, 281 parts by weight of MOO3 was combined with 3209 parts of alumina (2% silica in 98% alumina) and 639 parts of new commercially available alumina-containing Ni-Mo-P catalyst and combined together in a team. - grinding ment. With the milling equipment in operation, 2905 parts deionized water, nickel solution and 19 parts nitric acid (69.8% concentration) were added to the mixture in the milling equipment. The mixture was ground for a total of 35 minutes. The mixture had a pH of 4.18 and a LOI of 56.6 weight percent. The mixture was then extruded using 1.3mm trilobal dies to form 1.3mm trilobal extrudate particles. The extruded particles were then air dried over a period of several hours at a temperature of 100 ° C.

Aliquots of the dried extrudate particles were calcined in air each for a period of two hours at 426 ° C (800 ° F), 538 ° C (1000 ° F), and 649 ° C (1200 ° F). The final calcined mixture contained 2.2 weight percent nickel metal (2.8 wt% as NiO), 7.9 weight percent molybdenum metal (11.85 wt% as MoO2), 0.34% wt. phosphorus (0.55 wt% phosphorus pentoxide), and 84.8 weight percent 2% silica / alumina. Table 4 below shows some properties of the dried extruded particles that were calcined at each of the calcining temperatures.

Table 4 - Properties of Dry Extruded for Different Calcination Conditions.

Properties 426 0C (800 0F) 538 0C (1000 0F) 649 0C (1200 ° F) Crushing Strength, Ib / mm 5.63 5.72 5.03 Aqueous Pore Volume, mL / g 0.63 0 , 61 0.64 Pore Size Distribution Hg - Hg <70 A 34.1 24.2 11.2 70-100 A 60.4 69.3 75.4 100-130 A 2.6 3.2 9.6 130-150 A 0.6 0.7 0.9 150-180 A 0.8 0.8 0.8 180-350 A 1.4 1.4 1.6 350 A + 0.1 0.4 0.5 Average pore diameter, Á 74 79 90 Total pore volume, Hg, cc / g 0.57 0.60 0.59 Surface area, m2 / g 323 315 272

Example IV (Constant Reactor Temperature Example)

This Example describes one of the methods used to perform the catalyst tests described in Example III. This method provides processing of a supply having significant sulfur and asphalt contents to produce a product having reduced sulfur and asphalt contents and a liquid product that is stable. The reactor temperature was kept constant throughout these reactions and the sulfur content, asphalt content and liquid product quality were monitored.

A multi-drum reactor was used to conduct this test. The heating block contained four parallel tubular reactors each of which was a 15 mm (0.59 inch) ID by 600 mm (23.625 inch) length tube in 321 stainless steel. A single temperature control was used to control the heater block, which involved all four reactors. Each of the tubular reactors was loaded into a 30 cm3 bed arrangement of Catalyst B placed at the bottom of the catalyst bed and 6 cm3 of a commercially available hydrodemetallization catalyst placed at the top of the catalyst bed. One of the reactors was loaded with a commercially available alumina supported nickel and molybdenum hydrodesulphurization catalyst product from Criterion Catalyst Company designated as RN-650 (Catalyst C) as used in the other runs and a commercial HDM catalyst in the remaining bottom section. .

The stacked catalyst bed catalyst was activated by feeding into the ambient pressure a 5% v H2S and 95% v H2 gas mixture to the reactor at a rate of 30 SLPH while incrementally increasing the reactor temperature at a rate of 37 ° C. .80 ° C (100 ° F) / h 204.4 ° C (400 ° F). The catalyst bed was maintained at 204.4 ° C (400 ° F) for two hours, and then the temperature was incrementally increased at a rate of 37.8 ° C (100 ° F) / h to a temperature of 315.5 ° C (600 ° F), where it was held for two hours followed again by an incremental increase in temperature at a rate of 10 ° C (50 ° F) / h to a temperature of 371.10 ° C (700 ° F) where it was held for two hours before cooling the catalyst bed temperature to 204.40 ° C (400 ° F).

The supply loaded to the reactor was crude oil from the Middle East. Supply distillation properties as determined by ASTM Method D7169 are shown in Table 5. Table 6 presents some other supply properties.

Table 5 - Supply Distillation

% p Temperature, 0C (0F) IBP 351 (664) 399 (750) 437 (819) 40 472 (882) 50 510 (950) 60 554 (1029) 70 602 (1116) 80 657 (1215) 90 725 (1337 ) FBP 733 (1351) Table 6 - Other Supply Properties Property Value Micro-Carbon Residue (MCR) 11.4 Sulfur (% w) 4.012 Nickel (ppm) 16.7 Vanadium (ppm) 59 538 0C (1000 0F) + (% v) 43.5

The supply was charged to the reactors along with hydrogen gas. The

were maintained at a pressure of 13,100 kPa (1900 psig), and the supply was charged to the reactors at a rate to provide the net hourly space velocity (LHSV) of 0.6 h "1 and the hydrogen was charged at a rate of 534 m3 / m3 (3,000 SCF / bbl) Reactor temperatures were set at 385 0C (725 0F) for approximately one month and then raised to 400 0C (752 ° F) for the remainder of the period.

Graphs (the estimated linear function based on experimental data) of the product P-value as a function of the asphalt conversion of the supply to the process using inventive catalyst B and comparative catalyst are shown in Figure 1. As can be seen from the data shown in Figure 1, inventive catalyst B provides product stability as reflected by the P-value which is significantly higher than comparative catalyst C. At both operating temperatures In this case, the inventive catalyst provides greater asphalt conversion and higher product P-value. The comparative catalyst provides a less stable product than the inventive catalyst when asphalt conversion approaches 65%, which provides a stable product at significantly higher asphalt conversion.

Example V

This Example V describes the preparation of Catalyst D and a comparable catalyst.

captive E.

Catalyst D

Catalyst D was prepared by first combining 4047 parts by weight of 2% silica interstage alumina, 378 parts by weight of Ni (NC) 3 ^ nickel nitrate dissolved in 138 parts by weight of deionized water, and 418 parts by weight of molybdenum trioxide (MoO3) powder inside a Muller mixer. A total of 3807 parts by weight of water was added to these components during mixing. The components were mixed for approximately 45 minutes. The mixture had a pH of 4.75 and a LOI of 59.6 weight percent. The mixture was then extruded using 1.3mm trilobal dies to form 1.3mm trilobal extrudate particles. The extruded particles were then air dried over a period of several hours at a temperature of 100 ° C.

Aliquots of the dried extrudate particles were calcined in air each for a period of two hours at 538 0C (1000 0F), 677 0C (1250 0F), 704.4 0C (1300 0F), or 732.2 0C (1350 ° F). The final calcined mixture contained 2.2 weight percent nickel metal (2.8 wt% as NiO), 7.9 weight percent molybdenum metal (11.85 wt% as MOO3) and 85.45 weight percent 2% silica / alumina. Table 7 below shows some properties of the dried extrudate particles that were calcined at the calcination temperature of 677 ° C (1250 ° F). Table 7 - Properties of Dry and Calcined Extruded

Properties 677 0C (1250 0F) Crushing Strength, Ib / mm 3.81 Aqueous Pore Volume, mL / g 0.75 Pore Size Distribution Hg - Hg <70 A 5.5 70-100 A 53.6 100 -130 A 33.6 130-150 A 2.1 150-180 A 1.4 180-350 A 2.6 350 A + 1.2 Average Pore Diameter, A 98 Total Pore Volume, Hg1 cc / g 0.695 Area surface, ItiiVg 261

Catalyst E

Comparative catalyst E was produced by combining 4104 parts alumina powder with 127 parts nickel as nickel hydroxide and grinding rapidly. With the grinder in operation, 4104 parts of deionized water were added and the mixture in the grinder was ground for 55 minutes. Then molybdenum as ammonium di molybdate (ie a molybdenum salt) is ground for another five minutes. The mixture had a pH of 7.23 and a LOI of 59 weight percent. The mixture was then extruded using 1.3mm trilobal dies to form 1.3mm trilobal extrudate particles. The extruded particles were then air dried over a period of several hours at a temperature of 100 ° C.

Aliquots of the dried extrudate particles were calcined in air each for a period of two hours at 538 ° C (1000 ° F) and 649 ° C (1200 ° F). The final calcined mixture contained 2.2 weight percent nickel metal (2.8 wt% as NiO), 7.9 weight percent molybdenum metal (11.85 wt% as MoO3) and 85.35 weight percent of alumina. Table 8 below shows some properties of the dried extruded particles that were calcined at the calcination temperature of 677 0C (1250 0F).

Table 8 - Properties of Dry and Calcined Extruded

Properties 649 0C (1200 0F) Crushing Strength, Ib / mm 3.57 Pore Aqueous Volume, ml_ / g 0.87 Pore Size Distribution Hg - Hg <70 A 3.3 70-100 A 29.8 100 -130 A 58.9 130-150 A 2.6 150-180 A 1.6 180-350 A 2.3 350 A + 1.5 Average Pore Diameter, A 0.69 Total Pore Volume, Hg, cc / g 105 Surface area m2 / g 254.1

Example Vl (Constant Temperature Extended Period Test) This Example Vl describes one of the methods used to perform the catalyst tests described in Example V. This method provides processing of a supply having significant sulfur and MCR contents to produce a product having low sulfur content. The reactor temperature was kept constant throughout these reactions and the sulfur content of the product was monitored.

A multi-drum reactor was used to conduct this test. The heating block contained four parallel tubular reactors each of which was a 15 mm (0.59 inch) ID by 600 mm (23.625 inch) length tube in 321 stainless steel. A single temperature control was used to control the heater block, which involved all four reactors. Each of the tubular reactors was loaded into a 30 cm3 bed arrangement of the catalyst to be tested (or catalyst D or E) placed at the bottom of the catalyst bed and 6 cm3 of a commercially available hydrodemetallization catalyst placed on top of the catalyst bed.

The stacked catalyst bed catalyst was activated by feeding into the ambient pressure a 5% v H2S and 95% v H2 gas mixture to the reactor at a rate of 30 SLPH while incrementally increasing the reactor temperature at a rate of 37 ° C. .80 ° C (100 ° F) / h to 204.40 ° C (400 ° F).

The catalyst bed was kept at 204.4 ° C (400 ° F) for two hours, and then the temperature was incrementally increased at a rate of 37.8 ° C (100 ° F) / h to a temperature of 315 ° C. 50 ° C (600 ° F), where it was held for two hours followed again by an incremental increase in temperature at a rate of 10 ° C (50 ° F) / h to a temperature of 371.1 (700 ° F), where it was was maintained for two hours before cooling the catalyst bed temperature to 204.40 ° C (400 ° F).

The supply loaded to the reactor was a raw from the Middle East. The distillation properties of the supply as determined by the ASTM D7169 Method are shown in Table 9. Table 10 presents some other supply properties.

Table 9 - Supply Distillation

% p Temperature, 0C (0F) IBP 351 (664) 399 (750) 437 (819) 40 472 (882) 50 510 (950) 60 554 (1029) 70 602 (1116) 80 657 (1215) 90 725 (1337 ) FBP 733 (1351) Table 10 - Other Supply Properties Property Value Micro-Carbon Residue (MCR) 11.4 Sulfur (% w) 4.012 Nickel (ppm) 16.7 Vanadium (ppm) 59 538 0C (1000 0F) + (% v) 43.5

The supply was charged to the reactors along with hydrogen gas. The reactors were maintained at a pressure of 13,100 kPa (1900 psig), and the supply was charged to the reactors at a rate to provide the net hourly space velocity (LHSV) of 0.6 h "1 and hydrogen was charged to a rate of 3,000 SCF / bbl Reactor temperatures were set either at 385 0C (725 0F) or 400 0C (752 0F).

Graphs of the relative values of Weighted Average Bed Temperature (WABT) would be required for 88 wt% hydrodesulfurization of the supply as a function of run time for the inventive catalyst Deo comparative catalyst. As can be seen from the data presented in Figure 1, the inventive catalyst D exhibits catalytic activity over time that is significantly higher than the comparative catalyst E activity.

Claims (13)

A method of producing a highly stable catalyst for hydrocarbon sulfurization of heavy hydrocarbons, said method characterized by the fact that it comprises: co-agglutination of an inorganic oxide material, molybdenum trioxide, and a nickel compound to form a mixture; transforming said mixture into a particle; and calcining said particle to provide a calcined mixture. A method according to claim 1, characterized in that said calcination step is conducted under a controlled temperature condition in which the calcination temperature is in the range of about 600 ° C (1112 ° F) to about 760 ° C (1400 ° F) for a period of calcination that is effective to provide said calcined mixture having a desired pore structure. A method according to claim 2, characterized in that said desired pore structure includes a pore size distribution for said calcined mixture such that at least 70% of the total pore volume of said mixture is. Calcined is in the pores of said calcined mixture having a pore diameter in the range of 70 angstroms to 150 angstroms. A method according to claim 1, 2 or 3, characterized in that said mixture consists essentially of molybdenum trioxide, a nickel compound, and an inorganic oxide material. A method according to claim 1, 2, 3 or 4, characterized in that said mixture has a material absence of a molybdenum salt compound. A method according to claim 1, 2, 3, 4 or 5, characterized in that said co-agglutination step is conducted such that said mixture has a pH that is maintained in the range of 3 to 6. . A method according to claim 1, 2, 3, 4, 5 or 6, characterized in that said calcined mixture has a molybdenum content in the range of 4 weight percent to 18 weight percent. weight with the weight percent being based on molybdenum as MoO3 and the total weight of the calcined mixture, and a nickel content in the range of 1 weight percent to 5.1 weight percent with the weight percent being based in nickel as NiO and the total weight of the calcined mixture. 8. Highly stable heavy hydrocarbon hydrodesulfurization catalyst, characterized in that it comprises: a calcined mixture produced by calcining a particle formed of a mixture comprising molybdenum trioxide, a nickel compound, and an inorganic oxide material. Highly stable heavy hydrocarbon hydrodesulfurization catalyst according to claim 8, characterized in that said calcined mixture has a molybdenum content in the range of 4 weight percent to 18 weight percent. with the weight percent being based on molybdenum as MoO3 and the total weight of the calcined mixture, and a nickel content in the range of 1 weight percent to 5.1 weight percent with the weight percent being based on nickel as NiO and the total weight of the calcined mixture. Highly stable heavy hydrocarbon hydrodesulfurization catalyst according to claim 8 or 9, characterized in that said calcined mixture has a pore size distribution such that at least 70% of the total pore volume of the said calcined mixture is in the pores of said calcined mixture having a pore diameter in the range of 70 angstroms to 150 angstroms. Highly stable heavy hydrocarbon hydrodesulfurization catalyst according to claim 8, 9 or 10, characterized in that said calcined mixture has a property such that when used in the desulfurization of a heavy hydrocarbon supply results in a desulphurised product having a P-value of more than 1,5. A process for desulphurizing a heavy hydrocarbon supply, said process comprising: contacting, under appropriate conditions for heavy hydrocarbon desulphurization, said heavy hydrocarbon supply with any of the catalysts as defined in claims 8. 11 or any of the catalysts produced by the methods as defined in claims 1 to 7. Process according to claim 12, characterized in that said heavy hydrocarbon supply has a heavy hydrocarbon supply P-value of less than 1 and said treated hydrocarbon product has a hydrocarbon P-value. treated above 1.25.